EP4073186A1 - Matériaux isolants minéraux hydrophobes - Google Patents

Matériaux isolants minéraux hydrophobes

Info

Publication number
EP4073186A1
EP4073186A1 EP19821071.8A EP19821071A EP4073186A1 EP 4073186 A1 EP4073186 A1 EP 4073186A1 EP 19821071 A EP19821071 A EP 19821071A EP 4073186 A1 EP4073186 A1 EP 4073186A1
Authority
EP
European Patent Office
Prior art keywords
mineral
amino
radicals
radical
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19821071.8A
Other languages
German (de)
English (en)
Other versions
EP4073186B1 (fr
Inventor
Dominik JANTKE
Robert SCHRÖCK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP4073186A1 publication Critical patent/EP4073186A1/fr
Application granted granted Critical
Publication of EP4073186B1 publication Critical patent/EP4073186B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2213/00—Glass fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • the invention relates to hydrophobic mineral insulation materials containing at least one amino-functional one
  • Organosilicon compound with an amine number in the range from 0.05 to 0.40 and a process for their production and the use of amino-functional organosilicon compounds with an amine number in the range from 0.05 to 0.40 for rendering mineral insulation materials water-repellent.
  • a typical mineral insulation material is, for example, mineral wool.
  • Mineral wool is produced from the melt, procedures for this are well known, e.g. W02019 / 025706.
  • the binder or binders and the hydrophobizing component and dust binder and optionally further components are generally sprayed onto the still hot fibers directly after the fiber formation step on what are known as spinners.
  • Mineral wool in a freshly produced state is basically hydrophilic. This is particularly the case if phenol-formaldehyde-resin-based binders are not used.
  • Green binders based on organic, renewable raw materials, such as starch (e.g. WO2019 / 025672A1, Saint-Gobain), as well as the waiver of binders for the so-called "blowing wool” (e.g.
  • WO2014 / 044900A1 Acoustic Scandinavia
  • Mineral wool is usually made hydrophobic before being used as an insulating material. This can be done, for example, by reactive or non-reactive organosilicon compounds, usually polydimethylsiloxanes or silicone resins.
  • CN104402211A describes the use of SILRES ® BS 1042, an aqueous emulsion of a
  • Polydiethylsiloxane. W02019 / 043078A1 describes the use of SILRES ® BS 45, a solvent-free silicone resin emulsion.
  • the organosilicon compounds used have little interaction with the mineral fibers.
  • the hydrophobing agent In order to achieve a homogeneous coverage, the hydrophobing agent must therefore be applied directly after the manufacturing process of the fibers, especially when the fiber is very hot, in order to break the emulsion and distribute the silicone as homogeneously as possible on the fiber.
  • the dosage must also be chosen to be relatively high.
  • the invention relates to hydrophobic mineral insulation materials containing at least one amino-functional organosilicon compound with an amine number in the range from 0.05 to 0.40.
  • Mineral insulation materials are to be understood as meaning both those of natural and synthetic origin. Examples are expanded clay, calcium silicates such as vermiculite, mineral foam,
  • Perlite foam glass, mineral wool such as rock wool and glass wool. These materials are usually used for insulation in the form of fibers, granules, mats, panels or other molded parts.
  • the mineral wool insulation materials include, for example, artificial glass fibers, glass fibers, ceramic fibers, basalt fibers, stone fibers, etc.
  • the mineral wool insulation materials can be in any form, e.g. as panels, mats, or as a binder-free variant as so-called "blowing wool” for blown-in insulation.
  • Mineral wool is preferably used as the mineral insulation material, and glass wool, rock wool and "blowing wool” are particularly preferably used as the mineral insulation material.
  • the mineral insulation materials can contain binders or be free of binders; the presence of binders has no influence on the technical effect of the invention.
  • Typical binders for example for glass or rock wool, are phenol-formaldehyde, melamine-formaldehyde, or carbohydrate-based binders (e.g. starch-based).
  • the mineral insulation materials optionally contain further components such as dust binders, for example in the form of mineral oil emulsions, or adhesion promoters, such as silanes with amino side chains or silanes with glycidoxy side chains or silanes with ureido side chains.
  • the amino-functional organosilicon compound must have an amine number in the range from 0.05 to 0.40.
  • the amine number is preferably in a range from 0.10 to 0.20.
  • the amine number is the amount of potassium hydroxide (KOH) in mg, which is equivalent to the amine content of 1 g of substance. This can be determined, for example, by potentiometric titration or titration against bromophenol blue, as described in DIN 53176. In the case of mixtures of amino-functional organosilicon compounds, there is thus an average amine number for the mixture.
  • KOH potassium hydroxide
  • the amino-functional organosilicon compound can ligomers an O or polymeric organosilicon compound, it may be linear or branched.
  • the amino groups can be randomly distributed in the molecule or be arranged terminally. It can contain other reactive groups such as hydrolyzable groups (for example alkoxy groups).
  • the amino-functional organosilicon compound is preferably at least one compound of the formula (I) wherein the indices a i b, b ' ; c, c ', c'', d, d', d '' and d '''the
  • the radical R is a divalent, linear, unbranched or branched Ci-Ci 8 -hydrocarbon radical
  • the radicals R ' are independently selected from the group consisting of (i) hydrogen, (ii) unsubstituted or with at least one fluorine, chlorine or bromine atom or a hydroxyl group or a Ci-C 5 alkoxy group substituted Ci-Ci s -hydrocarbon radical, or (iii) unsubstituted or with at least one fluorine, chlorine or bromine atom or a hydroxyl group or a Ci-C 5 alkoxy group-substituted Ci- Cie acyl radical.
  • the radicals R 1 are independently a Ci-C6-alkyl radical, in particular a methyl radical; and in formula (II) the index a assumes the value 1, the index n assumes the value 2, the radicals R 'are hydrogen, and the radical R is a divalent Ci-Ce hydrocarbon radical, in particular a propylene radical.
  • Amino-functional organosilicon compounds are known per se and can be produced, inter alia, as described in EP1580215 or DE2339761, e.g. by reacting silanol-terminated silanes or polydimethylsiloxanes with amino-functional silanes.
  • Amino-functional organosilicon compounds are also commercially available, for example as silicone oils or in the form of emulsions.
  • Amino-functional organosilicon compounds having an amine number in the range from 0.05 to 0.40 are commercially available as emulsions such as SILRES BS ® 1340 by Wacker Chemie AG.
  • the invention also relates to the use of amino-functional organosilicon compounds with an amine number in the range from 0.05 to 0.40 for rendering mineral insulation materials water-repellent.
  • the mineral insulation materials are preferably selected from expanded clay, calcium silicates such as vermiculite, mineral foam, perlites, foam glass, mineral wool such as rock wool and glass wool.
  • the amino-functional organosilicon compound in the form of aqueous emulsions is preferably used to render mineral insulation materials water repellent.
  • Another subject matter is a process for the production of the hydrophobic mineral insulation materials comprising the steps: (A) providing an aqueous emulsion containing at least one amino-functional organosilicon compound with an amine number in the range from 0.05 to 0.40,
  • an emulsion comprises both the preparation of a corresponding emulsion and the use of commercially available emulsions.
  • Commercially available emulsions can be used unchanged, but they can also be diluted or the pH can be changed.
  • Emulsions containing at least one amino-functional organosilicon compound with an amine number in the range from 0.05 to 0.40 are usually based on the following components:
  • (C) optionally further constituents, such as, for example, emulsifiers, acids, biocides, thickeners, film formers, preservatives, silanes.
  • Preferred emulsions are usually based on the following components:
  • constituents such as biocides, thickeners, film formers, preservatives, silanes, for example.
  • anionic, nonionic, cationic or amphoteric emulsifiers can be used as emulsifiers, both individually and as mixtures of various emulsifiers, with which it has also been possible to prepare aqueous emulsions of organopolysiloxanes to date.
  • anionic emulsifiers examples include:
  • Alkyl sulfates especially those with a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) or propylene oxide units (PO) .
  • EO ethylene oxide
  • PO propylene oxide units
  • sulfonates especially alkyl sulfonates with 8 to 18 carbon atoms, alkylarylsulfonates with 8 to 18 carbon atoms, taurides, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms; if appropriate, these alcohols or alkylphenols can also be ethoxylated with 1 to 40 EO units.
  • Phosphoric acid partial esters and their alkali and ammonium salts especially alkyl and alkaryl phosphates with 8 to 20 carbon atoms in the organic radical, alkyl ether or alkaryl ether phosphates with 8 to 20 carbon atoms in the alkyl or alkaryl radical and 1 to 40 EO Units.
  • non-ionic emulsifiers are:
  • Polyvinyl alcohol which still contains 5 to 50%, preferably 8 to 20% of vinyl acetate units, with a degree of polymerization of 500 to 3000.
  • Alkyl polyglycol ethers preferably those with 3 to 40 EO units and alkyl radicals of 8 to 20 carbon atoms.
  • Alkylaryl polyglycol ethers preferably those with 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl radicals.
  • Ethylene oxide / propylene oxide (EO / PO) block copolymers preferably those with 8 to 40 EO or PO units.
  • Natural substances and their derivatives such as lecithin, lanolin, saponins, cellulose; Cellulose alkyl ethers and
  • Carboxyalkyl celluloses the alkyl groups of which each have up to 4 carbon atoms.
  • Polar groups containing in particular the elements O, N, C, S, P, Si, containing linear organo (poly) siloxanes, in particular those with alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.
  • cationic emulsifiers are:
  • Quaternary alkyl and alkylbenzene ammonium salts especially those whose alkyl groups have 6 to 24 carbon atoms, especially the halides, sulfates, phosphates and acetates.
  • Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts especially those whose alkyl chain has up to 18 carbon atoms, especially the halides, sulfates, phosphates and acetates.
  • amphoteric emulsifiers are particularly suitable as amphoteric emulsifiers:
  • Long-chain substituted amino acids such as N-alkyl-di (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salts.
  • Betaines such as N- (3-acylamidopropyl) -N, N-dimethylammonium salts with a Cg-Cig-acyl radical and alkylimidazolium betaines or quaternized alkyl or substituted alkyl derivatives of N, N-dimethylglycine.
  • Preferred emulsifiers are nonionic emulsifiers, in particular the polyvinyl alcohols or alkyl polyglycol ethers listed above under 5 and 6.
  • the emulsifier can consist of one of the abovementioned emulsifiers or a mixture of two or more of these emulsifiers; it can be used in pure form or as solutions of one or more emulsifiers in water or organic solvents.
  • the emulsifier can preferably be used in amounts in a range from 0.1 to 60% by weight, particularly preferably in a range from 0.5 to 30% by weight, based in each case on the total weight of amino-functional organosilicon compounds.
  • the emulsions can be produced by all common standard processes.
  • silanes known to the person skilled in the art as adhesion promoters can be used as silanes. These can in particular be silanes with amino side chains or silanes with glycidoxy side chains or silanes with ureido side chains.
  • Bringing into contact can take place by all common techniques known to the person skilled in the art, such as, for example, by spraying, dipping, brushing, pouring, etc.
  • the bringing into contact is preferably carried out by spraying or dipping.
  • Bringing into contact can take place once or several times; the same or a different emulsion can be used.
  • the drying can be carried out by all common techniques known to the person skilled in the art, such as, for example, air drying, infrared, contact drying, or in particular circulating air drying.
  • the pH value of the emulsion is usually in a range from 3 to 9; the pH value is preferably in the slightly acidic range from 4 to 6.
  • the active content of the emulsion used is not essential.
  • the active content of commercially available emulsions is usually in a range from 20% by weight to 70% by weight. Before it is brought into contact, it is also possible to dilute the emulsion with water and / or the above-mentioned components such as for example binders, dust binders or other components. When brought into contact, the emulsion should have an active content of at least 0.01% by weight, preferably 0.1% by weight.
  • the mineral insulation material can be in any form, e.g. as binder-free mineral wool ("blowing wool”), as binder-containing fibers, as mats, as panels or as other shaped bodies.
  • binder-free mineral wool blowing wool
  • binder-containing fibers as mats, as panels or as other shaped bodies.
  • the amino-functional organosilicon compound is preferably at least one compound of the general formula (I)
  • Ci-Cis hydrocarbon radical or (iii) unsubstituted or with at least one fluorine, chlorine or bromine atom or one
  • Ci-Cs-alkoxy group Hydroxy group or a Ci-Cs-alkoxy group of substituted Ci-
  • Cis acyl residue
  • the method according to the invention opens up the possibility of post-treating mineral wool that has already been produced.
  • SILRES ® BS 1042 aqueous emulsion of an OH-terminated, reactive polydimethylsiloxane, active content 60% by weight.
  • SILRES ® BS 1052 aqueous emulsion of a trimethylsilyl-terminated, non-reactive polydimethylsiloxane, active content 60% by weight.
  • SILRES ® BS 1340 pH 7: aqueous emulsion of an amino-functional polydimethylsiloxane, active content 60% by weight.
  • SILRES ® BS 1340 pH 5: aqueous emulsion of an amino-functional polydimethylsiloxane, active content 60% by weight. The pH was adjusted to 5 with acetic acid for the examples.
  • the contact angle was measured using a device from KRÜSS DSA 30. To measure the contact angle, 8 drops of water were placed on the test specimen and the contact angle was determined.
  • the experiments are suitable for simulating the water repellency of mineral wool surfaces.
  • the amino-functional emulsion SILRES ® BS 1340 shows a very fast and strong expression of the hydrophobicity, which is particularly strong at a slightly acidic pH value.
  • the examples (1-4) show very good spreading behavior, i.e. very good and rapid distribution directly on the mineral surface. The result is a very good long-term hydrophobicity due to the high interaction with the mineral surface.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matériaux isolants minéraux hydrophobes contenant au moins un composé organosilicié à fonction amino qui présente un indice d'amine compris entre 0,05 et 0,40.
EP19821071.8A 2019-12-11 2019-12-11 Matériaux isolants minéraux hydrophobes Active EP4073186B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2019/084712 WO2021115593A1 (fr) 2019-12-11 2019-12-11 Matériaux isolants minéraux hydrophobes

Publications (2)

Publication Number Publication Date
EP4073186A1 true EP4073186A1 (fr) 2022-10-19
EP4073186B1 EP4073186B1 (fr) 2023-04-19

Family

ID=68887416

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19821071.8A Active EP4073186B1 (fr) 2019-12-11 2019-12-11 Matériaux isolants minéraux hydrophobes

Country Status (4)

Country Link
US (1) US20230002275A1 (fr)
EP (1) EP4073186B1 (fr)
CN (1) CN114787302A (fr)
WO (1) WO2021115593A1 (fr)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5629691B2 (fr) 1972-08-11 1981-07-10
US20050148752A1 (en) * 2002-05-03 2005-07-07 Klaassens Lars I. Amino-functional polysiloxanes and their use in coatings
DE102004014218A1 (de) 2004-03-23 2005-10-13 Wacker-Chemie Gmbh Verfahren zur Herstellung von aminofunktionellen Organopolysiloxanen
DE102009054566A1 (de) 2009-12-11 2010-11-11 Wacker Chemie Ag Hydrophobe Wärmedämmung
FR2976582B1 (fr) * 2011-06-17 2014-12-26 Saint Gobain Isover Composition d'encollage pour laine minerale a faible emission de composes organiques volatils, et produits isolants obtenus.
DE102012201167A1 (de) * 2012-01-27 2013-08-01 Evonik Industries Ag Mischungszusammensetzung enthaltend aminofunktionelle Siloxane, hydrophobePartikel und hochmolekulare Silicone sowie dessen Verwendung zur Lederbehandlung
WO2014044900A1 (fr) 2012-09-21 2014-03-27 Acoustic Scandinavia Oy Machine pour laine à souffler et procédé permettant d'améliorer la qualité de la laine à souffler et les performances de la machine de soufflage
FR3069463B1 (fr) 2017-07-31 2020-07-17 Saint-Gobain Isover Installation de fabrication de laine minerale et dispositif de projection d’une composition d’encollage equipant une telle installation
FR3069536B1 (fr) 2017-07-31 2020-07-17 Saint-Gobain Isover Procede de fabrication de laine minerale
EA202090538A1 (ru) 2017-08-30 2020-06-22 Роквул Интернэшнл А/С Применение продукции из минеральной ваты
EP4201907A1 (fr) * 2018-04-16 2023-06-28 CertainTeed Corporation Matériaux isolants en laine minérale revêtus de silicone et leurs procédés de fabrication et d'utilisation

Also Published As

Publication number Publication date
WO2021115593A1 (fr) 2021-06-17
US20230002275A1 (en) 2023-01-05
CN114787302A (zh) 2022-07-22
EP4073186B1 (fr) 2023-04-19

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